At the Limits of Isolobal Bonding: π-Based Covalent Magnetism in MnHg.

Magnetic ordering in inorganic materials is generally considered to be a mechanism for structures to stabilize open shells of electrons. The intermetallic phase MnHg represents a remarkable exception: its crystal structure is in accordance with the 18- bonding scheme and non-spin-polarized density functional theory (DFT) calculations show a corresponding pseudogap near its Fermi energy. Nevertheless, it exhibits strong antiferromagnetic ordering virtually all the way up to its decomposition temperature. In this Article, we examine how these two features of MnHg coexist through the development of a DFT implementation of the reversed approximation Molecular Orbital (raMO) analysis. In the non-spin-polarized electronic structure, the DFT-raMO approach confirms that MnHg adheres to the 18- rule: its chains of Mn atoms are linked through isolobal triple bonds, with three electron pairs being shared at each Mn-Mn contact in one σ-type and two π-type functions. Because each Mn atom has 6 isolobal Mn-Mn bonds, it achieves a filled 18-electron count at the compound's electron concentration of 18 - 6 = 12 electrons/Mn. A pseudogap thus occurs at the Fermi energy. Upon the introduction of antiferromagnetic order, the original pseudogap widens and deepens, suggesting enhancement of a stabilizing effect already present in the nonmagnetic state. A raMO analysis reveals that antiferromagnetism enlarges the gap by allowing diradical character to enter into the Mn-Mn isolobal π bonds, reminiscent of the dissociation of a classic covalent bond. Antiferromagnetism is accompanied by residual bonding in the π system, making MnHg a vivid realization of the concept of covalent magnetism.